Triboluminescent materials and devices

ABSTRACT

This invention relates to various phosphine oxides and their use in applications which exploit the triboluminescent effect.

[0001] This invention relates to novel Triboluminescent (TL) materialsand their use in devices which exploit the triboluminescent effect.

[0002] Triboluminescent materials are known—(L M Sweeting & J L Guido,J. of Luminescence, 33, (1985), p167, N Kitamura et al, Chem Phys Letts,125, (1986), p360, B P Shandra, et al Pramana-J Phys, 29, (1987), p399,C R Hurt, et al Nature, 212, (1966), p179; L M Sweeting & A L Rheingold,J Am Chem Soc, 109, (1987), p2652 M B Hocking, et al, J. ofLuminescence, 43, (1989), p309). Chinese Chemical Letters, vol 11, no 7pp635-38, 2000 discloses a number of compounds that exhibitmechanoluminescence (ML). The property of mechanoluminescence iseffectively the same property as triboluminescence. More specificallytwo 1:1 binuclear (europium and lanthanum) β-diketonate complexes aredisclosed. The complexes further comprise 1,10-phenanthroline and ananion of thenoyltrifluoroacetone (HTTA). Soden in J. Appl. Phys., 32,(1961) 750 discloses the effects of rare-earth substitutions on thefluorescence of Terbium Hexa-Antipyrine tri-iodide.

[0003] Triboluminescence is the effect seen when a material emits lightwhen particles of the material are damaged/fractured or strained.

[0004] PCT GB96/02778 and corresponding U.S. Pat. No. 5,905,260 describethe use of triboluminescent compounds in an environment where they areused to detect damage to objects.

[0005] The following references disclose a number of fluorescentmaterials: EP 0744451, EP 0556005, U.S. Pat. No. 5,658,494, U.S. Pat.No. 3,551,345, PCT/GB98/01773, chemical abstracts 128:148933,103:226494, 101:45857.

[0006] Preferably for use in damage sensing equipment triboluminescentcompounds exhibit some or all of the following properties: Brightemission

[0007] High stability to temperature and high melting point

[0008] Compatibility with structural and adhesive resins

[0009] Emission at wavelengths which are different from those providedby known materials

[0010] Emission of light having other features distinguishable fromknown materials, such as luminescence lifetime, bandwidth etc.

[0011] Clearly it is also advantageous that triboluminescent compounds,if they are to be used commercially, are not prohibitively expensive.

[0012] There is a continued need for triboluminescent materials for usein such an environment and it is an object of the present inventioninter alia to provide alternative compounds suitable for use in a rangeof applications/devices which are capable of exploiting thetriboluminescence effect particularly sensing damage applications.

[0013] The current invention provides for, inter alia, the use of arange of compounds in a number of devices/applications which exploit thetriboluminescent effect.

[0014] According to a first aspect of the present invention materials offormula I are provided:

[0015] wherein

[0016] x is 1 or 2

[0017] M is selected from Europium, Terbium, Dysprosium and Samarium;

[0018] R1, R2 and R3 are independently of each other selected fromphenyl, naphthyl, H and C1-C6 branched or straight chain alkyl,thiophene and C1-C6 fluorinated alkyl wherein the fluorination may be in1 or all positions or any intermediate value, substituted phenyl whereinthe substituents are independently selected from C1-C4 straight orbranched chain alkyl, Cl, Br, F, I and the phenyl group may besubstituted in 1, 2 or 3 positions;

[0019] R4 and R5 are independently of each other selected from phenyl,tolyl, naphthyl, C1-C6 branched or straight chain alkyl and substitutedphenyl wherein the substituents are independently selected from C1-C4straight or branched chain alkyl and the phenyl group may be substitutedin 1, 2 or 3 positions;

[0020] R6 is selected from phenyl, tolyl, naphthyl, C1-C6 branched orstraight chain alkyl, —(CH₂)_(n)P(O)R7 R8, wherein n=1 to 4 and —N═(P R7R8 R9), wherein R7, R8 and R9 are independently selected from phenyl,naphthyl, C1-C6 branched or straight chain alkyl and substituted phenylwherein the substituents are independently selected from C1-C4 straightor branched chain alkyl and the phenyl group may be substituted in 1, 2or 3 positions;

[0021] R6 is also selected from substituted phenyl wherein thesubstituents are independently selected from C1-C4 straight or branchedchain alkyl and the phenyl group may be substituted in 1, 2 or 3positions;

[0022] It is understood in the definition of R6 that the phosphine oxidegroup, [included in —(CH₂)_(n)P(O)R7 R8] if present, may be coordinatedto the metal atom M or to another equivalent metal atom as a bridginggroup.

[0023] Preferably

[0024] R1, R2 and R3 are independently of each other selected fromphenyl, and C1-C4 branched or straight chain alkyl,

[0025] R4 and R5 are independently of each other selected from phenyl,tolyl and C1-C6 branched or straight chain alkyl,

[0026] R6 is selected from phenyl, tolyl, C1-C6 branched or straightchain alkyl, and 2-diphenylphosphinooxyethyl.

[0027] According to a second aspect of this invention a method of makingpaper that emits light when torn and/or pressed and/or gripped and/orfolded comprises the steps of coating and/or impregnating the paper withtriboluminescent material according to the first aspect of the presentinvention.

[0028] When coating and/or impregnating the paper it may be necessary toapply the triboluminescent material in one or more of a number of ways,for example:

[0029] in an adhesive composition, in addition the triboluminescentmaterial may be glued onto the paper either directly and/or in anencapsulant such as a polymer;

[0030] in a solvent followed by solvent evaporation;

[0031] by melting the triboluminescent material such that it soaks intothe paper;

[0032] by incorporating the triboluminescent material together with thepulp, fibre etc., during manufacture of the paper.

[0033] Preferably the solvent will be an organic solvent though thiswill be a function of the solvation properties of the triboluminescentmaterial.

[0034] Examples of suitable polymers for use in encapsulation includethe following:

[0035] Acrylic and methacrylic resins, polyimides, polyamides,melamine/formaldehyde resins, urea formaldehyde resins, epoxy resins,poly(p-xylylene), gelatin, poly(lactic acid), polyester resins and alkydresins.

[0036] Typical adhesives include:

[0037] Epoxy adhesives based on adducts of bisphenol-A andepichlorhydrin cured by polyamine or anhydride initiators, and similaradhesives based on other epoxides, UV curable and thermally curableadhesives based on acrylic, vinylic, styrenic, or thiol/ene monomersystems, cyanoacrylate adhesives, pressure sensitive adhesives, hot meltadhesives, latex based adhesives, PVA adhesives, solvent basedadhesives, urea formaldehyde and melamine formaldehyde adhesives,anaerobic adhesives, bis-diallyamine derived adhesives etc.

[0038] In addition to the adhesive and triboluminescent material theadhesive composition may also comprise one or more of the followingadditional reagents such as solvents, dispersants, plasticisers, curingagents, dyes, fillers, stabilisers, anti-oxidants etc as is understoodin the art. The compositions may include water as a solvent ordispersant or an organic solvent such as dichloromethane, acetone,tetrahydrofuran etc. may be present in order to ensure that thecomposition is homogenous and will spread well.

[0039] According to a third aspect of this invention paper is providedwhich comprises one or more triboluminescent materials according to thefirst aspect of the present invention such that the papertriboluminesces when the paper is torn and/or pressed and/or grippedand/or folded.

[0040] Such paper is obtainable by the method of the second aspect ofthe invention.

[0041] For all of the above aspects of the invention the term paper isalso taken to include paper-like products such as cardboard,kitchen-roll, tissue and the like.

[0042] According to a fourth aspect of the invention a productcomprising the paper of the third aspect of the invention is provided.

[0043] According to a fifth aspect of this invention an adhesivecomposition comprising an adhesive and one or more triboluminescentmaterials according to the first aspect of the present invention isprovided.

[0044] According to a sixth aspect of this invention a method ofadhering two surfaces together comprises the steps of:

[0045] applying an adhesive composition to one or more surfaces andbringing the surfaces into contact such that adhesion occurs wherein theadhesive composition comprises an adhesive and one or moretriboluminescent materials according to the first aspect of the presentinvention.

[0046] According to a seventh aspect of this invention a method ofmaking adhesive tape that flashes when used comprises the steps of:

[0047] selecting a substantially transparent substrate,

[0048] optionally depositing an adhesion promoter on the substrate,

[0049] depositing an adhesive composition comprising a triboluminescentmaterial according to the first aspect of the present invention on tothe substrate,

[0050] optionally drying the adhesive composition,

[0051] optionally depositing a further laminating sheet on top of theadhesive composition

[0052] before or after any drying stage.

[0053] The laminating sheet, if applied, may be treated with a releaselayer.

[0054] By flashes when used it is meant that the adhesive tape may flashwhen it is removed from a roll of adhesive tape or it may flash when itis removed from the object to which it has been applied. The adhesivetape may also flash when it is cut. How many times a particular piece ofadhesive tape flashes will depend on the nature of the triboluminescentmaterials used and the adhesive and the substrate to which it has beenadhered.

[0055] Drying may be carried out using any of the known techniques—theseinclude:

[0056] Solvent removal, removal of a dispersant phase, chemicalpolymerisation or cross linking, chemical reaction or condensation andmay be aided by known methods such as application of heat or UV light.

[0057] The substrate may comprise triboluminescent material itself,typically this would be carried out during formation of the substrate.

[0058] There are various uses to which the adhesive compositions andmethods of the present invention may be put. Included are adhesivecompositions when used on envelopes and tape and the like for indicatingwhether or not an envelope or package has been previously opened.Alternatively, seals on containers may compriseadhesive/triboluminesecent compositions according to the presentinvention so it is evident whether or not a container has been tamperedwith or damaged such that the seal has been broken in some way. For someof these particular type applications the adhesive and triboluminescentmaterials may with advantage be selected such that the composition onlytriboluminesces once.

[0059] Hence an eighth aspect of this invention provides a method fordetecting tampering of a sealed article comprising the steps of:

[0060] coating a part of an unsealed article with an adhesivecomposition,

[0061] sealing the article,

[0062] wherein the adhesive composition further comprises one or moretriboluminescent materials according to the first aspect of the presentinvention such that on breaking the seal triboluminescence will beobserved.

[0063] The article may be any type of suitable container, for example anenvelope or packaging or a bottle and top.

[0064] In the above method it is also possible for theadhesive/triboluminescent mixture to be applied once the article hasbeen sealed in some way. An example of this could be a bottle with ascrew top wherein the adhesive/triboluminescent mixture could be addedonce the top has been screwed on to the bottle. The mixture could alsobe added before and after the sealing.

[0065] The present invention also provides for opening packages,envelopes and the like with added aesthetic appeal. It is an objectiveof the present invention to provide aesthetic effects in relation toadhesives/adhesive tape/paper, paper-like products through the use oftechnical structures and/or other technical means.

[0066] Further aspects of the invention include articles produced by theabove methods.

[0067] Typical adhesives include:

[0068] Epoxy adhesives based on adducts of bisphenol-A andepichlorhydrin cured by polyamine or anhydride initiators, and similaradhesives based on other epoxides, UV curable and thermally curableadhesives based on acrylic, vinylic, styrenic, or thiol/ene monomersystems, cyanoacrylate adhesives, pressure sensitive adhesives, hot meltadhesives, latex based adhesives, PVA adhesives, solvent basedadhesives, urea formaldehyde and melamine formaldehyde adhesives,anaerobic adhesives, bis-diallyamine derived adhesives etc.

[0069] In addition to the adhesive and triboluminescent material theadhesive composition may also comprise one or more of the followingadditional components such as solvents, wetting agents, flow modifiers,plasticisers, curing agents, dyes, fillers, stabilisers, anti-oxidantsetc as is understood in the art. The compositions may include water as asolvent or dispersant or an organic solvent such as dichloromethane,acetone, tetrahydrofuran etc. may be present in order to ensure that thecomposition is homogenous and will spread well.

[0070] According to a ninth aspect of this invention a damage-sensingdevice comprises at least one light sensor and at least onetriboluminescent material according to the first aspect of the currentinvention.

[0071] The light sensor may be connected directly to thetriboluminescent material or via light guiding means such as opticalfibres.

[0072] The sensor may be embedded within a structure, such as acomposite plastics material, or fixed externally to such a structure.Several sensors may be embedded within one structure. Light output fromthe triboluminescent material may be detected directly, or such lightoutput may be absorbed by photo excitable dye material whose subsequentluminescence is detected. Different triboluminescent material describedby the present invention and or different dyes may be used in differentparts of a structure so that damage location is readily determined fromthe wavelength of emission. The detector may be directly connected toeach different triboluminescent or dye material, or one or moredetectors used with filters or wavelength detection means to determinethe location of damage at several sites.

[0073] Additionally the damage site may be located by timing receipt ofpulses. The intensity of emission may also be measured to give anindication of the severity of impact and hence damage.

[0074] The light guiding means may be single or multimode opticalfibres, optical transparent sheet or slab within a composite material.The sheet material may have waveguides defined by rib, indiffusion, oretching etc, and may contain secondary emitters.

[0075] The detectors may be photo multipliers, photo diodes, as singledetectors or in arrays.

[0076] Use of the materials of the present invention may be incorporatedinto the devices described in U.S. Pat. No. 5,905,260 the contents ofwhich are incorporated herein by reference.

[0077] The invention will now be described, by way of example only, withreference to the accompanying drawings of which:—

[0078]FIG. 1 is a sectional view of a sensor embedded within astructure;

[0079]FIG. 2 is similar to and a variation of FIG. 1;

[0080]FIG. 3 is a sectional view of two sensors embedded within astructure, with optical fibre readout to a single detector;

[0081]FIG. 4 is a sectional view of a sensor mounted on a surface of astructure;

[0082]FIG. 5 is a sectional view of several triboluminescent materialsand a light guiding layer embedded within a structure;

[0083]FIG. 6 is similar to that of FIG. 5, but in addition has adifferent photo excitable dye associated with each triboluminescentmaterial;

[0084]FIG. 7 is a perspective view of a sensor employing threedifferently doped fibres each directing light from severaltriboluminescent materials to a single detector.

[0085] As seen in FIG. 1 a sensor 1 is embedded in a composite material2 such as a glass or carbon fibre matrix layered material. The sensor 1comprises a small crystal 3 of a triboluminescent CTL) material asdescribed by the present invention held within a cavity 4 by epoxy resin5 and optically connected by optical cement such as a UV curing glue 6from the Norland™ range to an optical fibre 7 which transmits light toan externally mounted detector 8. This detector 8 may be a photo diodeor part of an array linked to several crystals.

[0086] The composite material 2, may have different triboluminescentmaterials 3 with their characteristic emissions arranged at differentpositions within the composite 2. The detectors 8 detect such differentwavelengths thereby giving positional information about damage location

[0087] In operation, e.g. in an aircraft, impact of objects on thecomposite 2 above a predetermined known energy level will damage thecrystal 3 causing it to emit light; high impact energy results in higherlight output. The detected light may either be transmitted as a signaldirectly to the pilot if a serious damage had occurred or stored bycomputer and read by a maintenance crew at a later stage for damagerepair. If the recorded detection indicates composite damage, then thatpart of the composite may be repaired or replaced before the nextaircraft flight.

[0088] Thus several different materials constructed as in FIG. 1 may beused as shown in different parts of a structure and a single detectorused. In this case the detector must be able to distinguish differentwavelengths to indicate which area of the structure has received damage.

[0089]FIG. 2 is similar to FIG. 1 and given like reference numeral. Inthis example the optical fibre 7 optically connects to glue 5 holdingthe crystal 3 within the cavity 4. The glue 5 is optically transparentand may be a polymer matrix.

[0090]FIG. 3 shows different TL crystals 10, 11 (two only shown, but maybe many more) located in cavities 12, 13 in different parts of acomposite material 14. A single detector 15 connects with each crystal10, 11 via an optical fibre network 16 and is sensitive to the differentemissions of the crystals 10, 11, and can therefore indicate thelocation of any damage. Such an arrangement reduces the number ofcavities needed within the composite material 14.

[0091]FIG. 4 shows how a sensor 20 can be mounted externally on acomposite material 21. As before one or more TL crystals 22 areencapsulated within an optically transparent glue or resin 23 andcoupled to a detector 24 via an optical fibre 25. When a plurality ofdifferent crystals 22 are used, the detector 24 is arranged todistinguish between their different emissions wavelengths to give anindication of damage location. A protective layer 26 of opaque materialcovers the glue 23.

[0092]FIG. 5 shows a composite material 30 in which a layer 31 of aguiding material is sandwiched between two layers 32, 33. Embeddedwithin the light guiding layer 31 are one or more TL crystals 34. Adetector 35 is mounted on the edge of the composite material 30.Suitable materials for the light guiding layer 31 include:—UV curingglues, sol-gel, optically transparent polymers, resins or glues.

[0093]FIG. 6 shows a composite material 40 in which a layer 41 of alight guiding material is sandwiched between two layers 42, 43. Embeddedwithin the layer 41 are three TL crystals 44, 45, 46. Above each crystal44, 45, 46 is a volume of three different photo excitable dyes 47, 48,49 contained within a second layer 50 of a light guiding material. Adetector 51 is sensitive to the outputs of each dye volume 47, 48, 49.When damage occurs, an appropriate crystal 44, 45, 46 will emit lightand cause an associated dye volume 47, 48, 49 respectively to emit lightat a characteristic wavelength which is guided by the layer 50 to thedetector 51.

[0094]FIG. 7 shows a composite layer material 60 in which several TLcrystals 61, 62, 63 are embedded in rows within a layer 64. Opticalfibres 66, 67, 68 containing photo excitable dyes are in optical contactwith these rows of crystals 61, 62, 63 and connect via an optical fibrenetwork 69 to one or more detectors 70. The fibres 66, 67, 68 areembedded in an optically transparent layer 71 and covered with aprotective layer 72 of composite fibre. The crystals 61, 62, 63 may beone of the adducts of the present invention, the fibres 66, 67, 68 maybeglass single or multi mode fibres, or polymer fibres; the glues may beRS™ bipax epoxy, Araldite™ fast setting, or Norland UV curing flues.

[0095] In a modification of FIG. 7 an additional set of differentlydoped optical fibres is arranged in columns so that an x,y matrix ofdifferently doped optical fibres lies within a composite material. Thecolumn fibres are connected to one or more detectors as in FIG. 7.Signals from these two detectors indicate where in the matrix, light isbeing received.

[0096] A flashing form of paper, (e.g. writing paper, tissue orcardboard) according to the present invention may be fabricated asfollows. Paper is soaked in a solution of triboluminescent material andany excess solvent is evaporated off. The paper may then be torn, foldedor crumpled to test for a triboluminescent effect.

[0097] An alternative method of fabrication involves melting thetriboluminescent material and allowing the melt to soak into the paper.

[0098] An alternative method of fabrication involves gluingtriboluminescent material to the surface of the paper, alternatively thetriboluminescent material is encapsulated, for example, in polymer whichmay then be coated on to the surface of the paper. Examples of suitablepolymer include poly vinyl alcohol. The polymer may be applied whilststill in monomer form and subsequently cured.

[0099] A flashing form of adhesive tape according to the presentinvention may be fabricated as follows. An adhesive compound which maybe cured via any of the known methods of curing including by uvpolymerisation and a triboluminescent material are placed on to a sheetof plastic material. A further sheet of plastic is pressed on top of thefirst sheet, sandwiching the adhesive/triboluminescent mixture. Thesheets plus mixture are then subject to curing such that the monomerpolymerises—it may be the case that an amount of the monomer remainsunpolymerised. In order to assess the tape the sheets may be pulledapart to reveal bright flashes.

[0100] It is not necessarily the case that the adhesive is a monomersystem—any type of adhesive known to those skilled in the art would besuitable. The mixture need not necessarily require curing.

[0101] Example triboluminescenrt complexes-according to the inventionwere prepared by the methods described below. In assessing the relativebrightnesses of triboluminescent materials, it is understood by thoseskilled in the art that quantitative comparisons are made difficult bythe dependancy of the triboluminescent emission intensity on suchfactors as the crystalline particle size and crystal habit of thesample, the force applied to the sample, traces of different impuritieswhich may occur in the sample, the geometry of the optical detector andits wavelength sensitivity. For the purpose of evaluating the usefulnessof the compounds of the invention, a semi-quantitative scale wasemployed based on observation of the triboluminescent emission from thesamples by eye, while the materials in the form of crystalline powderswere crushed in a soda lime glass sample tube under hand pressure with astainless steel spatula. The brightness is then assessed according tothe highest level of ambient illumination, in the presence of which thetriboluminescent emission becomes visible. The scale employed is:Brightness Maximum ambient light for Scale observation 10 Full daylight9 Diffuse daylight 8 Bright room lighting 7 Subdued room lighting 6 Dimartificial light 5 Semi-darkness 4 Darkness, without dark adaptation ofthe eye 3 Darkness, with up to 2 mins dark adaptation 2 Darkness, withup to 10 mins dark adaptation 1 Visible with fully dark adapted eye 0 Noobservable triboluminescence

[0102] Compounds of this invention may be prepared by means which areapparent to those skilled in the art. Known metal tris β-diketonates maybe reacted with one or two molar quantities of substituted phosphineoxides. Phosphine oxides are known materials which are in many casescommercially available. In cases where the phosphine oxide is not acommercial product, but the phosphine is available, the phosphine may beoxidised to the phosphine oxide, for example by treatment with an excessof hydrogen peroxide in ethanol. An alternative synthesis comprises thecombination of the β-diketone, the phosphine oxide and a salt of themetal in appropriate molar ratios with a small excess of a base. Asuitable base includes potassium ethoxide, when the reaction isconveniently carried out in solution in ethanol. Preferably the reagentsand solvents used in the synthesis, irrespective of the route chosen,are substantially anhydrous. Purification of the products may be carriedout by recrystallisation from a solvent eg., from anhydrous ethanol ordry toluene.

[0103] Example synthesis: Tris 2,2,6,6-tetramethylheptanedionato terbiumtriphenylphosphine oxide adduct

[0104] Terbium tris 2,2,6,6-tetramethylheptanedionate (1 g) andtriphenylphosphine oxide (0.393 g) were added to anhydrous ethanol (3ml). The mixture was warmed to dissolve the solid, and then raised toboiling for 10 minutes. The solution was cooled to room temperature andthen to 0° C. to induce crystallisation of the product. The off-whitesolid was filtered off and recrystallised from anhydrous ethanol anddried in vacuo at 60° C. to yield tris 2,2,6,6-tetramethylheptanedionatoterbium triphenylphosphine oxide adduct (0.9 g) as a white solid.

[0105] The following compounds were synthesised in the same way:

[0106] Tris acetylacetonato terbium triphenylphosphine oxide adduct

[0107] Tris acetylacetonato terbium tritolylphosphine oxide adduct

[0108] Tris acetylacetonato terbium 1-naphthyldiphenylphosphine oxideadduct

[0109] Tris acetylacetonato terbium bisdiphenylphosphinoethane bisP-oxide adduct

[0110] Tris acetylacetonato terbium bisdiphenylphosphinopropane bisP-oxide adduct

[0111] Tris acetylacetonato terbium bisdiphenylphosphinobutane bisP-oxide adduct

[0112] Tris acetylacetonato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0113] Tris dibenzoylmethanato terbium triphenylphosphine oxide adduct

[0114] Tris dibenzoylmethanato terbium tritolylphosphine oxide adduct

[0115] Tris dibenzoylmethanato terbium 1-naphthyidiphenylphosphine oxideadduct

[0116] Tris dibenzoylmethanato terbium bisdiphenylphosphinoethane bisP-oxide adduct

[0117] Tris dibenzoylmethanato terbium bisdiphenylphosphinopropane bisP-oxide adduct

[0118] Tris dibenzoylmethanato terbium bisdiphenylphosphinobutane bisP-oxide adduct

[0119] Tris dibenzoylmethanato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0120] Tris thenoyltrifluoroacetonato terbium triphenylphosphine oxideadduct

[0121] Tris thenoyltrifluoroacetonato terbium tritolylphosphine oxideadduct

[0122] Tris thenoyltrifluoroacetonato terbium1-naphthyldiphenylphosphine oxide adduct

[0123] Tris thenoyltrifluoroacetonato terbium bisdiphenylphosphinoethanebis P-oxide adduct

[0124] Tris thenoyltrifluoroacetonato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0125] Tris thenoyltrifluoroacetonato terbium bisdiphenylphosphinobutanebis P-oxide adduct

[0126] Tris thenoyltrifluoroacetonato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0127] Tris 2,2,6,6-tetramethylheptanedionato terbium triphenylphosphineoxide adduct brightness=4

[0128] Tris 2,2,6,6-tetramethylheptanedionato terbium tritolylphosphineoxide adduct

[0129] Tris 2,2,6,6-tetramethylheptanedionato terbium1-naphthyidiphenylphosphine oxide adduct

[0130] Tris 2,2,6,6-tetramethylheptanedionato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0131] Tris 2,2,6,6-tetramethylheptanedionato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0132] Tris 2,2,6,6-tetramethylheptanedionato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0133] Tris 2,2,6,6-tetramethylheptanedionato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0134] Tris 3-methylpentane-2,4-dionato terbium triphenylphosphine oxideadduct

[0135] Tris 3-methylpentane-2,4-dionato terbium tritolylphosphine oxideadduct

[0136] Tris 3-methylpentane-2,4-dionato terbium1-naphthyldiphenylphosphine oxide adduct

[0137] Tris 3-methylpentane-2,4-dionato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0138] Tris 3-methylpentane-2,4-dionato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0139] Tris 3-methylpentane-2,4-dionato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0140] Tris 3-methylpentane-2,4-dionato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0141] Tris 3-ethylpentane-2,4-dionato terbium triphenylphosphine oxideadduct

[0142] Tris 3-ethylpentane-2,4-dionato terbium tritolylphosphine oxideadduct

[0143] Tris 3-ethylpentane-2,4-dionato terbium1-naphthyldiphenylphosphine oxide adduct

[0144] Tris 3-ethylpentane-2,4-dionato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0145] Tris 3-ethylpentane-2,4-dionato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0146] Tris 3-ethylpentane-2,4-dionato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0147] Tris 3-ethylpentane-2,4-dionato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0148] Tris pivaloyltrifluoroacetonato terbium triphenylphosphine oxideadduct

[0149] Tris pivaloyltrifluoroacetonato terbium tritolylphosphine oxideadduct

[0150] Tris pivaloyltrifluoroacetonato terbium1-naphthyldiphenylphosphine oxide adduct

[0151] Tris pivaloyltrifluoroacetonato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0152] Tris pivaloyltrifluoroacetonato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0153] Tris pivaloyltrifluoroacetonato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0154] Tris pivaloyltrifluoroacetonato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0155] Tris trifluoroacetylacetonato terbium triphenylphosphine oxideadduct

[0156] Tris trifluoroacetylacetonato terbium tritolylphosphine oxideadduct

[0157] Tris trifluoroacetylacetonato terbium 1-naphthyldiphenylphosphineoxide adduct

[0158] Tris trifluoroacetylacetonato terbium bisdiphenylphosphinoethanebis P-oxide adduct

[0159] Tris trifluoroacetylacetonato terbium bisdiphenylphosphinopropanebis P-oxide adduct

[0160] Tris trifluoroacetylacetonato terbium bisdiphenylphosphinobutanebis P-oxide adduct

[0161] Tris trifluoroacetylacetonato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0162] Tris hexafluoroacetylacetonato terbium triphenylphosphine oxideadduct

[0163] Tris hexafluoroacetylacetonato terbium tritolylphosphine oxideadduct

[0164] Tris hexafluoroacetylacetonato terbium1-naphthyldiphenylphosphine oxide adduct

[0165] Tris hexafluoroacetylacetonato terbium bisdiphenylphosphinoethanebis P-oxide adduct

[0166] Tris hexafluoroacetylacetonato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0167] Tris hexafluoroacetylacetonato terbium bisdiphenylphosphinobutanebis P-oxide adduct

[0168] Tris hexafluoroacetylacetonato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0169] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumtriphenylphosphine oxide adduct

[0170] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumtritolylphosphine oxide adduct

[0171] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbium1-naphthyidiphenylphosphine oxide adduct

[0172] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0173] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0174] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0175] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0176] Tris 1-phenyl-1,3-butanedionato terbium triphenylphosphine oxideadduct

[0177] Tris 1-phenyl-1,3-butanedionato terbium tritolylphosphine oxideadduct

[0178] Tris 1-phenyl-1,3-butanedionato terbium1-naphthyldiphenylphosphine oxide adduct

[0179] Tris 1-phenyl-1,3-butanedionato terbiumbisdiphenylphosphinoethane bis P-oxide adduct

[0180] Tris 1-phenyl-1,3-butanedionato terbiumbisdiphenylphosphinopropane bis P-oxide adduct

[0181] Tris 1-phenyl-1,3-butanedionato terbiumbisdiphenylphosphinobutane bis P-oxide adduct

[0182] Tris 1-phenyl-1,3-butanedionato terbiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0183] Tris acetylacetonato europium triphenylphosphine oxide adduct

[0184] Tris acetylacetonato europium tritolylphosphine oxide adduct

[0185] Tris acetylacetonato europium 1-naphthyldiphenylphosphine oxideadduct

[0186] Tris acetylacetonato europium bisdiphenylphosphinoethane bisP-oxide adduct

[0187] Tris acetylacetonato europium bisdiphenylphosphinopropane bisP-oxide adduct

[0188] Tris acetylacetonato europium bisdiphenylphosphinobutane bisP-oxide adduct

[0189] Tris acetylacetonato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0190] Tris dibenzoylmethanato europium triphenylphosphine oxide adduct

[0191] Tris dibenzoylmethanato europium tritolylphosphine oxide adduct

[0192] Tris dibenzoylmethanato europium 1-naphthyldiphenylphosphineoxide adduct

[0193] Tris dibenzoylmethanato europium bisdiphenylphosphinoethane bisP-oxide adduct

[0194] Tris dibenzoylmethanato europium bisdiphenylphosphinopropane bisP-oxide adduct

[0195] Tris dibenzoylmethanato europium bisdiphenylphosphinobutane bisP-oxide adduct

[0196] Tris dibenzoylmethanato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0197] Tris thenoyltrifluoroacetonato europium triphenylphosphine oxideadduct

[0198] Tris thenoyltrifluoroacetonato europium tritolylphosphine oxideadduct

[0199] Tris thenoyltrifluoroacetonato europium1-naphthyldiphenylphosphine oxide adduct

[0200] Tris thenoyltrifluoroacetonato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0201] Tris thenoyltrifluoroacetonato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0202] Tris thenoyltrifluoroacetonato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0203] Tris thenoyltrifluoroacetonato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0204] Tris 2,2,6,6-tetramethylheptanedionato europiumtriphenylphosphine oxide adduct brightness=3

[0205] Tris 2,2,6,6-tetramethylheptanedionato europium tritolylphosphineoxide adduct

[0206] Tris 2,2,6,6-tetramethylheptanedionato europium1-naphthyldiphenylphosphine oxide adduct

[0207] Tris 2,2,6,6-tetramethylheptanedionato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0208] Tris 2,2,6,6-tetramethylheptanedionato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0209] Tris 2,2,6,6-tetramethylheptanedionato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0210] Tris 2,2,6,6-tetramethylheptanedionato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0211] Tris 3-methylpentane-2,4-dionato europium triphenylphosphineoxide adduct

[0212] Tris 3-methylpentane-2,4-dionato europium tritolylphosphine oxideadduct

[0213] Tris 3-methylpentane-2,4-dionato europium1-naphthyldiphenylphosphine oxide adduct

[0214] Tris 3-methylpentane-2,4-dionato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0215] Tris 3-methylpentane-2,4-dionato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0216] Tris 3-methylpentane-2,4-dionato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0217] Tris 3-methylpentane-2,4-dionato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0218] Tris 3-ethylpentane-2,4-dionato europium triphenylphosphine oxideadduct

[0219] Tris 3-ethylpentane-2,4-dionato europium tritolylphosphine oxideadduct

[0220] Tris 3-ethylpentane-2,4-dionato europium1-naphthyidiphenylphosphine oxide adduct

[0221] Tris 3-ethylpentane-2,4-dionato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0222] Tris 3-ethylpentane-2,4-dionato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0223] Tris 3-ethylpentane-2,4-dionato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0224] Tris 3-ethylpentane-2,4-dionato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0225] Tris pivaloyltrifluoroacetonato europium triphenylphosphine oxideadduct

[0226] Tris pivaloyltrifluoroacetonato europium tritolylphosphine oxideadduct

[0227] Tris pivaloyltrifluoroacetonato europium1-naphthyldiphenylphosphine oxide adduct

[0228] Tris pivaloyltrifluoroacetonato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0229] Tris pivaloyltrifluoroacetonato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0230] Tris pivaloyltrifluoroacetonato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0231] Tris pivaloyltrifluoroacetonato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0232] Tris trifluoroacetylacetonato europium triphenylphosphine oxideadduct

[0233] Tris trifluoroacetylacetonato europium tritolylphosphine oxideadduct

[0234] Tris trifluoroacetylacetonato europium1-naphthyldiphenylphosphine oxide adduct

[0235] Tris trifluoroacetylacetonato europium bisdiphenylphosphinoethanebis P-oxide adduct

[0236] Tris trifluoroacetylacetonato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0237] Tris trifluoroacetylacetonato europium bisdiphenylphosphinobutanebis P-oxide adduct

[0238] Tris trifluoroacetylacetonato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0239] Tris hexafluoroacetylacetonato europium triphenylphosphine oxideadduct

[0240] Tris hexafluoroacetylacetonato europium tritolylphosphine oxideadduct

[0241] Tris hexafluoroacetylacetonato europium1-naphthyldiphenylphosphine oxide adduct

[0242] Tris hexafluoroacetylacetonato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0243] Tris hexafluoroacetylacetonato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0244] Tris hexafluoroacetylacetonato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0245] Tris hexafluoroacetylacetonato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0246] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumtriphenylphosphine oxide adduct

[0247] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumtritolylphosphine oxide adduct

[0248] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europium1-naphthyidiphenylphosphine oxide adduct

[0249] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0250] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0251] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0252] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0253] Tris 1-phenyl-1,3-butanedionato europium triphenylphosphine oxideadduct

[0254] Tris 1-phenyl-1,3-butanedionato europium tritolylphosphine oxideadduct

[0255] Tris 1-phenyl-1,3-butanedionato europium1-naphthyldiphenylphosphine oxide adduct

[0256] Tris 1-phenyl-1,3-butanedionato europiumbisdiphenylphosphinoethane bis P-oxide adduct

[0257] Tris 1-phenyl-1,3-butanedionato europiumbisdiphenylphosphinopropane bis P-oxide adduct

[0258] Tris 1-phenyl-1,3-butanedionato europiumbisdiphenylphosphinobutane bis P-oxide adduct

[0259] Tris 1-phenyl-1,3-butanedionato europiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0260] Tris acetylacetonato samarium triphenylphosphine oxide adduct

[0261] Tris acetylacetonato samarium tritolylphosphine oxide adduct

[0262] Tris acetylacetonato samarium 1-naphthyidiphenylphosphine oxideadduct

[0263] Tris acetylacetonato samarium bisdiphenylphosphinoethane bisP-oxide adduct

[0264] Tris acetylacetonato samarium bisdiphenylphosphinopropane bisP-oxide adduct

[0265] Tris acetylacetonato samarium bisdiphenylphosphinobutane bisP-oxide adduct

[0266] Tris acetylacetonato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0267] Tris dibenzoylmethanato samarium triphenylphosphine oxide adduct

[0268] Tris dibenzoylmethanato samarium tritolylphosphine oxide adduct

[0269] Tris dibenzoylmethanato samarium 1-naphthyldiphenylphosphineoxide adduct

[0270] Tris dibenzoylmethanato samarium bisdiphenylphosphinoethane bisP-oxide adduct

[0271] Tris dibenzoylmethanato samarium bisdiphenylphosphinopropane bisP-oxide adduct

[0272] Tris dibenzoylmethanato samarium bisdiphenylphosphinobutane bisP-oxide adduct

[0273] Tris dibenzoylmethanato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0274] Tris thenoyltrifluoroacetonato samarium triphenylphosphine oxideadduct

[0275] Tris thenoyltrifluoroacetonato samarium tritolylphosphine oxideadduct

[0276] Tris thenoyltrifluoroacetonato samarium1-naphthyldiphenylphosphine oxide adduct

[0277] Tris thenoyltrifluoroacetonato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0278] Tris thenoyltrifluoroacetonato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0279] Tris thenoyltrifluoroacetonato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0280] Tris thenoyltrifluoroacetonato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0281] Tris 2,2,6,6-tetramethylheptanedionato samariumtriphenylphosphine oxide adduct brightness=1

[0282] Tris 2,2,6,6-tetramethylheptanedionato samarium tritolylphosphineoxide adduct

[0283] Tris 2,2,6,6-tetramethylheptanedionato samarium1-naphthyldiphenylphosphine oxide adduct

[0284] Tris 2,2,6,6-tetramethylheptanedionato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0285] Tris 2,2,6,6-tetramethylheptanedionato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0286] Tris 2,2,6,6-tetramethylheptanedionato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0287] Tris 2,2,6,6-tetramethylheptanedionato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0288] Tris 3-methylpentane-2,4-dionato samarium triphenylphosphineoxide adduct

[0289] Tris 3-methylpentane-2,4-dionato samarium tritolylphosphine oxideadduct

[0290] Tris 3-methylpentane-2,4-dionato samarium1-naphthyldiphenylphosphine oxide adduct

[0291] Tris 3-methylpentane-2,4-dionato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0292] Tris 3-methylpentane-2,4-dionato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0293] Tris 3-methylpentane-2,4-dionato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0294] Tris 3-methylpentane-2,4-dionato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0295] Tris 3-ethylpentane-2,4-dionato samarium triphenylphosphine oxideadduct

[0296] Tris 3-ethylpentane-2,4-dionato samarium tritolylphosphine oxideadduct

[0297] Tris 3-ethylpentane-2,4-dionato samarium1-naphthyidiphenylphosphine oxide adduct

[0298] Tris 3-ethylpentane-2,4-dionato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0299] Tris 3-ethylpentane-2,4-dionato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0300] Tris 3-ethylpentane-2,4-dionato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0301] Tris 3-ethylpentane-2,4-dionato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0302] Tris pivaloyltrifluoroacetonato samarium triphenylphosphine oxideadduct

[0303] Tris pivaloyltrifluoroacetonato samarium tritolylphosphine oxideadduct

[0304] Tris pivaloyltrifluoroacetonato samarium1-naphthyldiphenylphosphine oxide adduct

[0305] Tris pivaloyltrifluoroacetonato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0306] Tris pivaloyltrifluoroacetonato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0307] Tris pivaloyltrifluoroacetonato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0308] Tris pivaloyltrifluoroacetonato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0309] Tris trifluoroacetylacetonato samarium triphenylphosphine oxideadduct

[0310] Tris trifluoroacetylacetonato samarium tritolylphosphine oxideadduct

[0311] Tris trifluoroacetylacetonato samarium1-naphthyldiphenylphosphine oxide adduct

[0312] Tris trifluoroacetylacetonato samarium bisdiphenylphosphinoethanebis P-oxide adduct

[0313] Tris trifluoroacetylacetonato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0314] Tris trifluoroacetylacetonato samarium bisdiphenylphosphinobutanebis P-oxide adduct

[0315] Tris trifluoroacetylacetonato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0316] Tris hexafluoroacetylacetonato samarium triphenylphosphine oxideadduct

[0317] Tris hexafluoroacetylacetonato samarium tritolylphosphine oxideadduct

[0318] Tris hexafluoroacetylacetonato samarium1-naphthyldiphenylphosphine oxide adduct

[0319] Tris hexafluoroacetylacetonato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0320] Tris hexafluoroacetylacetonato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0321] Tris hexafluoroacetylacetonato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0322] Tris hexafluoroacetylacetonato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0323] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumtriphenylphosphine oxide adduct

[0324] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumtritolylphosphine oxide adduct

[0325] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samarium1-naphthyldiphenylphosphine oxide adduct

[0326] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0327] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0328] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0329] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0330] Tris 1-phenyl-1,3-butanedionato samarium triphenylphosphine oxideadduct

[0331] Tris 1-phenyl-1,3-butanedionato samarium tritolylphosphine oxideadduct

[0332] Tris 1-phenyl-1,3-butanedionato samarium1-naphthyidiphenylphosphine oxide adduct

[0333] Tris 1-phenyl-1,3-butanedionato samariumbisdiphenylphosphinoethane bis P-oxide adduct

[0334] Tris 1-phenyl-1,3-butanedionato samariumbisdiphenylphosphinopropane bis P-oxide adduct

[0335] Tris 1-phenyl-1,3-butanedionato samariumbisdiphenylphosphinobutane bis P-oxide adduct

[0336] Tris 1-phenyl-1,3-butanedionato samariumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0337] Tris acetylacetonato dysprosium triphenylphosphine oxide adduct

[0338] Tris acetylacetonato dysprosium tritolylphosphine oxide adduct

[0339] Tris acetylacetonato dysprosium 1-naphthyldiphenylphosphine oxideadduct

[0340] Tris acetylacetonato dysprosium bisdiphenylphosphinoethane bisP-oxide adduct

[0341] Tris acetylacetonato dysprosium bisdiphenylphosphinopropane bisP-oxide adduct

[0342] Tris acetylacetonato dysprosium bisdiphenylphosphinobutane bisP-oxide adduct

[0343] Tris acetylacetonato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0344] Tris dibenzoylmethanato dysprosium triphenylphosphine oxideadduct

[0345] Tris dibenzoylmethanato dysprosium tritolylphosphine oxide adduct

[0346] Tris dibenzoylmethanato dysprosium 1-naphthyidiphenylphosphineoxide adduct

[0347] Tris dibenzoylmethanato dysprosium bisdiphenylphosphinoethane bisP-oxide adduct

[0348] Tris dibenzoylmethanato dysprosium bisdiphenylphosphinopropanebis P-oxide adduct

[0349] Tris dibenzoylmethanato dysprosium bisdiphenylphosphinobutane bisP-oxide adduct

[0350] Tris dibenzoylmethanato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0351] Tris thenoyltrifluoroacetonato dysprosium triphenylphosphineoxide adduct

[0352] Tris thenoyltrifluoroacetonato dysprosium tritolylphosphine oxideadduct

[0353] Tris thenoyltrifluoroacetonato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0354] Tris thenoyltrifluoroacetonato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0355] Tris thenoyltrifluoroacetonato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0356] Tris thenoyltrifluoroacetonato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0357] Tris thenoyltrifluoroacetonato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0358] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumtriphenylphosphine oxide adduct brightness=4

[0359] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumtritolylphosphine oxide adduct

[0360] Tris 2,2,6,6-tetramethylheptanedionato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0361] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0362] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0363] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0364] Tris 2,2,6,6-tetramethylheptanedionato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0365] Tris 3-methylpentane-2,4-dionato dysprosium triphenylphosphineoxide adduct

[0366] Tris 3-methylpentane-2,4-dionato dysprosium tritolylphosphineoxide adduct

[0367] Tris 3-methylpentane-2,4-dionato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0368] Tris 3-methylpentane-2,4-dionato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0369] Tris 3-methylpentane-2,4-dionato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0370] Tris 3-methylpentane-2,4-dionato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0371] Tris 3-methylpentane-2,4-dionato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0372] Tris 3-ethylpentane-2,4-dionato dysprosium triphenylphosphineoxide adduct

[0373] Tris 3-ethylpentane-2,4-dionato dysprosium tritolylphosphineoxide adduct

[0374] Tris 3-ethylpentane-2,4-dionato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0375] Tris 3-ethylpentane-2,4-dionato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0376] Tris 3-ethylpentane-2,4-dionato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0377] Tris 3-ethylpentane-2,4-dionato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0378] Tris 3-ethylpentane-2,4-dionato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0379] Tris pivaloyltrifluoroacetonato dysprosium triphenylphosphineoxide adduct

[0380] Tris pivaloyltrifluoroacetonato dysprosium tritolylphosphineoxide adduct

[0381] Tris pivaloyltrifluoroacetonato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0382] Tris pivaloyltrifluoroacetonato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0383] Tris pivaloyltrifluoroacetonato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0384] Tris pivaloyltrifluoroacetonato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0385] Tris pivaloyltrifluoroacetonato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0386] Tris trifluoroacetylacetonato dysprosium triphenylphosphine oxideadduct

[0387] Tris trifluoroacetylacetonato dysprosium tritolylphosphine oxideadduct

[0388] Tris trifluoroacetylacetonato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0389] Tris trifluoroacetylacetonato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0390] Tris trifluoroacetylacetonato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0391] Tris trifluoroacetylacetonato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0392] Tris trifluoroacetylacetonato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0393] Tris hexafluoroacetylacetonato dysprosium triphenylphosphineoxide adduct

[0394] Tris hexafluoroacetylacetonato dysprosium tritolylphosphine oxideadduct

[0395] Tris hexafluoroacetylacetonato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0396] Tris hexafluoroacetylacetonato dysprosiumbisdiphenylphosphinoethane bis P-oxide adduct

[0397] Tris hexafluoroacetylacetonato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0398] Tris hexafluoroacetylacetonato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0399] Tris hexafluoroacetylacetonato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

[0400] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium triphenylphosphine oxide adduct

[0401] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium tritolylphosphine oxide adduct

[0402] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium 1-naphthyldiphenylphosphine oxide adduct

[0403] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium bisdiphenylphosphinoethane bis P-oxide adduct

[0404] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium bisdiphenylphosphinopropane bis P-oxide adduct

[0405] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium bisdiphenylphosphinobutane bis P-oxide adduct

[0406] Tris 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedionatodysprosium diphenyl(triphenylphosphinaza)phosphine oxide adduct

[0407] Tris 1-phenyl-1,3-butanedionato dysprosium triphenylphosphineoxide adduct

[0408] Tris 1-phenyl-1,3-butanedionato dysprosium tritolylphosphineoxide adduct

[0409] Tris 1-phenyl-1,3-butanedionato dysprosium1-naphthyldiphenylphosphine oxide adduct

[0410] Tris 1-phenyl-1,3-butanedionato dysprosiumbisdiphenylphosphinoethane bis. P-oxide adduct

[0411] Tris 1-phenyl-1,3-butanedionato dysprosiumbisdiphenylphosphinopropane bis P-oxide adduct

[0412] Tris 1-phenyl-1,3-butanedionato dysprosiumbisdiphenylphosphinobutane bis P-oxide adduct

[0413] Tris 1-phenyl-1,3-butanedionato dysprosiumdiphenyl(triphenylphosphinaza)phosphine oxide adduct

1. Compounds of formula I:

wherein x is 1 or 2 M is selected from Europium, Terbium, Dysprosium andSamarium; H and c1-C6 branched or straight chain alkyl, thiophene andC1-C6 fluorinated alkyl wherein the fluorination may be in 1 or allpositions or any intermediate value, substituted phenyl wherein thesubstituents are independently selected fro C1-C4 straight or branchedchain alkyl, Cl, Br, F, I and the phenyl group may be substituted in 1,2 or 3 positions; R4 and R5 are independently of each other selectedfrom phenyl, tolyl, naphthyl, C1-C6 branched or straight chain alkyl andsubstituted phenyl wherein the substituents are independently selectedfrom C1-C4 straight or branched chain alkyl and the phenyl group may besubstituted in 1, 2 or 3 positions; R6 is selected from phenyl, tolyl,naphthyl, C1-C6 branched or straight chain aklyl, −(CH₂)_(n)P(O) R7 R8,wherein n=1 to 4 and −N=(P R7 R8 R9), wherein R7, R8 and R9 areindependently selected from phenyl, naphthyl, C1-C6 branched or straightchain alkyl and substituted phenyl wherein the substituents areindependently selected from C1-C4 straight or branched chain alkyl andthe phenyl group may be substituted in 1, 2 or 3 positions; R6 is alsoselected from substituted phenyl wherein the substituents areindependently selected from C1-C4 straight or branched chain alkyl andthe phenyl group may be substituted in 1, 2 or 3 positions.
 2. Acompound according to claim 1 wherein when R6 is −(CH₂₎ _(n)P(O) R7 R8then the O is coordinated to the M group.
 3. A compound according toclaim 1 wherein when R6 is −(CH₂₎ _(n)P(O) R7 R8 then the O iscoordinated to another equivalent metal atom as a bridging group.
 4. Acompound according to any of claims 1-3 wherein R1, R2 and R3 areindependently of each other selected from phenyl, and C1-C4 branched orstraight chain alkul, R4 and R5 are independently of each other selectedfrom phenyl, tolyl and C1-C6 branched or straight chain alkyl, R6 isselected from phenyl tolyl, C1-C6 branched or straight chain alkyl, and2-diphenylphosphinooxyethyl.
 5. Use of a compound according to any ofclaims 1-4 as a triboluminescent material.
 6. A method of making paperthat emits light when torn and/or pressed and/or gripped and/or foldedcomprising the steps of coating and/or impregnating the paper withtriboluminescent material given by claims 1-3.
 7. A method according toclaim 6 wherein the triboluminescent material is applied by one or moreof the following methods: in an adhesive composition, and/or in anencapsulant; in a solvent followed by solvent evaporation; by meltingthe triboluminescent material such that it soaks into the paper; byincorporating the triboluminescent material together with the pulp,fibre during manufacture of the paper.
 8. A method according to claim 7wherein the triboluminescent material is applied in an adhesivecomposition and/or in an encapsulant wherein the encapsulant is apolymer which is selected from the following: acrylic and methacrylicresins, polyimides, polyamides, melamine/formaldehyde resins, ureaformaldehyde resins, epoxy resins, poly(p-xylylene), gelatin,poly(lactic acid), polyester resins and alkyd resins.
 9. A methodaccording to claim 7 wherein the triboluminescent material is applied inan adhesive composition and/or in an encapsulant wherein the adhesivecomposition may also comprise one or more of the following: solvents,dispersants, plasticisers, curing agents, dyes, fillers, stabilisers,anti-oxidants.
 10. Paper comprising one or more triboluminescentmaterial given by claims 1-3 such that the paper triboluminesces whenthe paper is tor and/or pressed and/or gripped and/or folded.
 11. Aproduct comprising the paper of claim
 10. 12. An adhesive compositioncomprising an adhesive and one or more triboluminescent materialaccording to claims 1-3.
 13. A method of adhering two surfacews togethercomprising the steps of: applying an adhesive composition to one or moresurfaces and bringing the surfaces into contact such that adhesionoccurs wherin the adhesice composition comprises an adhesive and one ormore triboluminescent material given by claims 1-3.
 14. A method ofmaking adhesive tape that flashes when used comprising the steps of:selecting a substantially transparent substrate, optionally depositingan adhesion promoter on the substrate, depositing an adhesivecomposition comprising a triboluminescent material given by claims 1-3on to the substrate, optionally drying the adhesive composition,optionally depositing a further laminating sheet on top of the adhesivecomposition before or after any drying stage.
 15. A method for detectingtampering of a sealed article comprising the steps of: coating a part ofan unsealed article with an adhesive composition, sealing the article,wherein the adhesive composition further comprises one or moretriboluminescent materials given by claims 1-3 such that on breaking theseal triboluminescence will be observed.
 16. A damage-sensing devicecomprising at least one light sensor and at least one triboluminescentmaterial given by claims 1-3.